EP3564029A1 - Verbundkörper aus metall/faser-verstärktem harzmaterial, verfahren zur herstellung davon und klebefolie - Google Patents

Verbundkörper aus metall/faser-verstärktem harzmaterial, verfahren zur herstellung davon und klebefolie Download PDF

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Publication number
EP3564029A1
EP3564029A1 EP17886111.8A EP17886111A EP3564029A1 EP 3564029 A1 EP3564029 A1 EP 3564029A1 EP 17886111 A EP17886111 A EP 17886111A EP 3564029 A1 EP3564029 A1 EP 3564029A1
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EP
European Patent Office
Prior art keywords
resin
bonding
fiber
metal member
reinforced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17886111.8A
Other languages
English (en)
French (fr)
Other versions
EP3564029A4 (de
Inventor
Hiroyuki Takahashi
Hideki Andoh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical and Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical and Materials Co Ltd filed Critical Nippon Steel Chemical and Materials Co Ltd
Publication of EP3564029A1 publication Critical patent/EP3564029A1/de
Publication of EP3564029A4 publication Critical patent/EP3564029A4/de
Withdrawn legal-status Critical Current

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    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
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    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive

Definitions

  • the present invention relates to, for example, a metal/fiber-reinforced resin material composite body in which a metal member made of a steel material and a resin material are laminated, a method for producing the same, and a bonding sheet.
  • Fiber-reinforced plastics made of reinforced fibers such as glass fibers and carbon fibers, and a matrix resin are widely used across consumer goods and industrial applications because they are lightweight and have excellent mechanical characteristics.
  • FRP Fiber-reinforced plastics
  • CFRP carbon fiber reinforced plastic
  • CFRP composite material of a metal member and a CFRP
  • thermosetting resin such as an epoxy resin
  • thermoplastic resin has also been studied for a bonding agent for combining a matrix resin of a fiber-reinforced resin material and a metal member in order to improving the processability and recyclability.
  • a method of adhering and bonding a fiber-reinforced resin material and a metal member the development of a technique for strengthening mainly adhesion between a metal member and a bonding agent has been actively performed.
  • Patent Literature 1 and Patent Literature 2 disclose techniques in which a bonding surface of a metal member is subjected to a surface roughening treatment to have specific surface shape parameters, a hard and highly crystalline thermoplastic resin is injected and molded, a bonding layer of an epoxy resin is provided on a metal member, and the bonding strength between the metal member and a CFRP is improved.
  • a roughened surface on a metal member surface that is chemically etched to have a special surface microstructure is filled with a hard and highly crystalline thermoplastic resin, and thus strength is exhibited. Therefore, a special treatment needs to be performed for roughening and rust prevention, and also, during combining, since it is necessary to perform a high temperature process due to problems of the melt viscosity and a high melting point, there are problems regarding productivity and costs.
  • Patent Literature 3 discloses a composite body of a reinforced fiber base material and a metal in which a bonding resin such as an epoxy resin is impregnated with a surface of a carbon fiber base material adhered to a metal member, and a thermoplastic resin is impregnated with the other surface to prepare a prepreg. According to this method, it is possible to provide an integrated and molded article having strong adhesion strength even when different members such as a fiber-reinforced resin material and a metal member are adhered.
  • an epoxy type thermosetting resin is used for a bonding agent layer, reinforced fibers are caused to penetrate into the bonding agent layer, and thus adhesion between a fiber-reinforced sheet and a metal layer is maintained. Therefore, a non-woven fabric made of fibers with a specific length need to be used as a reinforced fiber base material, and the reinforcing effect is limited compared to a unidirectional fiber-reinforced material and a cloth material.
  • Patent Literature 4 discloses a method of producing a sandwich structure with a steel plate using a CFRP molding material using a polyurethane resin matrix.
  • favorable moldability of a thermoplastic polyurethane resin is used, a crosslinking reaction is caused in a polyurethane resin after curing to form a thermosetting resin, and thereby high strength is achieved.
  • the polyurethane resin has low heat resistance, there are problems that it is difficult to apply it to members exposed to a high temperature, and its application is limited.
  • Patent Literature 5 discloses that a powder of a phenoxy resin or a resin composition in which a crystalline epoxy resin and an acid anhydride as a crosslinking agent are added to a phenoxy resin is applied to a reinforced fiber base material by a powder coating method to produce a prepreg, and this prepreg is molded and cured by heating and pressing to form a CFRP.
  • Patent Literature 5 it is suggested that an aluminum foil and a stainless steel foil can be laminated on the CFRP.
  • Patent Literature 5 since there is no example related to a composite body of a CFRP and a metal member, the mechanical strength such as the bending strength for the composite body has not been studied.
  • Patent Literature 6 proposes a method of producing a structure part for a vehicle body in which a composite material composed of a flat carrier material including a metal and a fiber-reinforced thermoplastic material and a support material formed of a thermoplastic material is heated, a rib structure is formed on the support material, and the carrier material is formed into a three-dimensional part.
  • Patent Literature 7 proposes a fiber-reinforced resin intermediate material which is used by being heated and pressurized in a laminated state and in which a reinforced fiber base material has voids opening on the outer surface, and a resin in the form of powder is in a semi-impregnated state.
  • the present invention provides a metal/fiber-reinforced resin material composite body in which a metal member and a fiber-reinforced resin material are firmly adhered and which is lightweight and has excellent processability and can be produced by a simple method and is inexpensive.
  • the inventors conducted extensive studies and as a result, found that it is possible to address the above problems by adhering a metal member and a fiber-reinforced resin material using a solidified product of a phenoxy resin (A) alone or a cured product of a bonding resin composition containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components, and thereby completed the present invention.
  • a metal/fiber-reinforced resin material composite body includes a metal member; a first fiber-reinforced resin material that is combined with the metal member; and a bonding resin layer which is laminated on at least one surface of the metal member and interposed between the metal member and the first fiber-reinforced resin material for bonding them together.
  • the bonding resin layer contains a solidified product of a phenoxy resin (A) alone or a cured product of a bonding resin composition containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components.
  • the bonding resin layer may be a second fiber-reinforced resin material including the solidified product as a matrix resin, or including the cured product and a reinforced fiber base material contained in the matrix resin.
  • the bonding resin composition in the metal/fiber-reinforced resin material composite body, may be a crosslinkable bonding resin composition which further contains an epoxy resin (B) in a range of 5 to 85 parts by weight with respect to 100 parts by weight of the phenoxy resin (A) and a crosslinking agent (C) containing an acid dianhydride.
  • the cured product may be a cross-linked cured product and a glass transition temperature (Tg) thereof may be 160 °C or higher.
  • the material of the metal member may be a steel material, an iron alloy or aluminum.
  • a metal/fiber-reinforced resin material composite body includes a metal member; a first fiber-reinforced resin material that is combined with the metal member; and a bonding resin layer which is laminated on at least one surface of the metal member and interposed between the metal member and the first fiber-reinforced resin material for bonding them together.
  • the bonding resin layer includes a cured product in a first cured state using a bonding resin containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components
  • a glass transition temperature (Tg) varies.
  • the bonding resin layer may be a second fiber-reinforced resin material containing a reinforced fiber base material in a matrix resin, and the matrix resin may be the cured product in a first cured state.
  • a bonding sheet bonds a metal member and a fiber-reinforced resin material.
  • the bonding sheet is a prepreg which includes a bonding resin composition that contains a phenoxy resin (A) alone or 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components; and a reinforced fiber base material.
  • a fourth aspect of the present invention is a method for producing a metal/fiber-reinforced resin material composite body including a metal member, a first fiber-reinforced resin material that is combined with the metal member, and a bonding resin layer which is laminated on at least one surface of the metal member and interposed between the metal member and the first fiber-reinforced resin material for bonding them together.
  • the production method includes a process in which a bonding resin composition containing a phenoxy resin (A) alone or 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components is applied to the metal member to form a coating film; and a process in which a first prepreg which is a precursor of the first fiber-reinforced resin material is disposed on the coating film, according to heating and pressing, the phenoxy resin (A) in the coating film is melted and then solidified or the bonding resin composition is melted and then cured, and thereby the bonding resin layer is formed, and the first fiber-reinforced resin material and the metal member are adhered and combined.
  • a fifth aspect of the present invention provides a method for producing a metal/fiber-reinforced resin material composite body which includes a metal member, a first fiber-reinforced resin material that is combined with the metal member, and a bonding resin layer which is laminated on at least one surface of the metal member and interposed between the metal member and the first fiber-reinforced resin material for bonding them together, and in which the bonding resin layer is a second fiber-reinforced resin material including a matrix resin and a reinforced fiber base material contained in the matrix resin.
  • the production method includes a process in which a fine powder of a phenoxy resin (A) alone or a bonding resin composition which contains 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components and is a solid at room temperature is attached to the reinforced fiber base material by powder coating to produce a second prepreg which is a precursor of the second fiber-reinforced resin material and has a resin composition proportion (RC) in a range of 20 to 50%; and a process in which the metal member, the second prepreg, and a first prepreg which is a precursor of the first fiber-reinforced resin material are laminated and disposed in this order, according to heating and pressing, the phenoxy resin (A) is melted and then solidified or the bonding resin composition is melted and then cured, and thereby the bonding resin layer is formed, and the first fiber-reinforced resin material and the metal member are adhered and combined.
  • a metal/fiber-reinforced resin material composite body in which a metal member and a fiber-reinforced resin material are firmly adhered with a bonding resin layer therebetween.
  • the metal/fiber-reinforced resin material composite body is lightweight and has excellent processability and can be produced by a simple method. For example, even if the metal member is a steel material subjected to an antirust treatment, the metal member and the fiber-reinforced resin material have high bonding strength without performing a special surface roughening treatment.
  • the metal/fiber-reinforced resin material composite body of the present invention as a lightweight and high-strength material can be suitably used for not only for cases for electrical and electronic components but also structural members in applications such as automobile members and aircraft members.
  • FIG. 1 and FIG. 2 are schematic views showing a cross-sectional structure of a metal-FRP composite body in a lamination direction as a metal/fiber-reinforced resin material composite body according to a first embodiment of the present invention.
  • a metal-FRP composite body 100 includes a metal member 101, an FRP layer 102 as a first fiber-reinforced resin material, and a bonding resin layer 103 interposed between the metal member 101 and the FRP layer 102.
  • the bonding resin layer 103 is a solidified product of a phenoxy resin (A) alone or a cured product of a bonding resin composition containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components.
  • a cured product in addition to a cured product in a first cured state which is solidified but it is not crosslinked after the phenoxy resin (A) and the like contained in the bonding resin composition are melted, it also includes a cross-linked cured product in a second cured state to be described below.
  • the FRP layer 102 includes a matrix resin 104 and a reinforced-fiber material 105 which is contained in and combined with the matrix resin 104.
  • the bonding resin layer 103 is provided in contact with at least one side surface of the metal member 101 and firmly bonds the metal member 101 to the FRP layer 102.
  • the bonding resin layer 103 and the FRP layer 102 may be formed on both surfaces of the metal member 101.
  • the metal member 101 may be disposed on both sides of a laminate including the bonding resin layer 103 and the FRP layer 102 therebetween.
  • the FRP layer 102 is formed using at least one or more FRP molding prepregs.
  • the FRP layer 102 is not limited to one layer, and may be formed into, for example, two or more layers as shown in FIG. 2 .
  • the thickness of the FRP layer 102, the number of FRP molding prepregs when the FRP layer 102 is formed into a plurality of layers, and the number of layers n of the FRP layer 102 can be appropriately set according to the purpose of use.
  • Respective layers of the FRP prepreg forming the FRP layer 102 may have the same configuration or different configurations. That is, the resin type of the matrix resin 104 constituting the FRP layer 102, the type, content, and the like of the reinforced-fiber material 105 may be different for each layer.
  • the FRP layer 102 may be molded in advance when combined with the metal member 101 or may be in a state of the FRP molding prepreg and is preferably in a latter state in which a more uniform FRP layer 102 can be formed.
  • the resin constituting the bonding resin layer 103 and the matrix resin 104 of the first FRP layer 102 in contact with the bonding resin layer 103 may be the same resin or different from each other.
  • the same resin refers to resins which are composed of the same components and have the same composition proportions
  • the same type of resin refers to resins which may have different composition proportions as long as the main components are the same.
  • the "same type of resin” includes “the same resin.”
  • the "main component” refers to a component of which a proportion is 50 parts by weight or more in 100 parts by weight of resin components.
  • the "resin components” include a thermoplastic resin, a thermosetting resin, and the like, but do not include a non-resin component such as a crosslinking agent.
  • FIG. 3 and FIG. 4 are schematic views showing a cross-sectional structure of a metal-FRP composite body as a metal/fiber-reinforced resin material composite body according to a second embodiment of the present invention.
  • a metal-FRP composite body 200 includes the metal member 101, the FRP layer 102 as a first fiber-reinforced resin material, and a bonding resin layer 103A interposed between the metal member 101 and the FRP layer 102.
  • the bonding resin layer 103A is a second fiber-reinforced resin material including a matrix resin 106 and a reinforced-fiber material 107 contained in and combined with the matrix resin 106.
  • the matrix resin 106 is a solidified product of a phenoxy resin (A) alone or a cured product of a bonding resin composition containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components.
  • the configuration of the FRP layer 102 is the same as in the first embodiment.
  • the bonding resin layer 103A is provided in contact with at least one side surface of the metal member 101, and firmly bonds the metal member 101 to the FRP layer 102.
  • the bonding resin layer 103A and the FRP layer 102 may be formed on both surfaces of the metal member 101.
  • the metal member 101 may be disposed on both sides of a laminate including the bonding resin layer 103A and the FRP layer 102 with therebetween.
  • the FRP layer 102 is configured of at least one or more FRP molding prepregs, and the FRP layer 102 is not limited to one layer, and may be formed into, for example, two or more layers as shown in FIG. 4 .
  • the number of layers n of the FRP layer 102 when the FRP layer 102 is formed into a plurality of layers can be appropriately set according to the purpose of use.
  • Respective layers of the FRP layer 102 may have the same configuration or different configurations. That is, the resin type of the matrix resin 104 constituting the FRP layer 102, and the type, content, and the like of the reinforced-fiber material 105 may be different for each layer.
  • the type of the resin constituting the matrix resin 106 of the bonding resin layer 103A may be the same as or different from the type of the resin of the matrix resin 104 of the first FRP layer 102 in contact with the bonding resin layer 103A.
  • the resin of the matrix resin 106 of the bonding resin layer 103A and the resin of the matrix resin 104 of the FRP layer 102 are the same or of the same type.
  • the thickness of the bonding resin layers 103 and 103A is, for example, preferably in a range of 3 to 100 ⁇ m, and more preferably in a range of 5 to 75 ⁇ m.
  • the thickness of the bonding resin layers 103 and 103A is less than 3 ⁇ m, bonding between the metal member 101 and the FRP layer 102 is insufficient, and sufficient mechanical strength cannot be obtained in the metal-FRP composite bodies 100 and 200.
  • the bonding resin layer 103 and 103A exceeds 100 ⁇ m, the bonding resin layer is in excess and thus a sufficient reinforcing effect of reinforced fibers in the metal-FRP composite bodies 100 and 200 cannot be obtained.
  • the material, shape, thickness, and the like of the metal member 101 are not particularly limited as long as it can be molded and processed by pressing and the like, and the shape is preferably a thin plate shape.
  • the material of the metal member 101 include iron, titanium, aluminum, magnesium and alloys thereof.
  • the alloy refers to, for example, an iron alloy (including stainless steel), a Ti alloy, an Al alloy, a Mg alloy, or the like. More preferable examples of the material of the metal member 101 include a steel material, an iron alloy, and aluminum, and most preferable examples thereof include steel materials.
  • Such a steel material examples include carbon steel, alloy steel, high tensile steel, and the like used for general structures and mechanical structures which are steel materials defined in the Japanese Industrial Standards (JIS) and the like.
  • Specific examples of such a steel material include cold rolled steel, hot rolled steel, a hot rolled steel plate material for an automobile structure, and a hot rolled high tensile steel plate material for automobile processing.
  • any surface treatment may be performed on the surface of the steel material.
  • the surface treatment include various plating treatments such as zinc plating and aluminum plating, chemical conversion treatments such as a chromate treatment and a non-chromate treatment, and a chemical surface roughening treatment using physical or chemical etching such as sand blasting, but the present invention is not particularly limited thereto.
  • a plurality of types of surface treatments may be performed.
  • at least an antirust treatment is preferably performed.
  • the primer include a silane coupling agent and a triazine thiol derivative.
  • the silane coupling agent include an epoxy-based silane coupling agent, an amino-based silane coupling agent, and an imidazole silane compound.
  • triazine thiol derivative examples include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium, 6-propyl-2,4-dithiolamino-1,3,5-triazine monosodium, and 2,4,6-trithiol-1,3,5-triazine.
  • the reinforced-fiber materials 105 and 107 used for the metal-FRP composite bodies 100 and 200 are not particularly limited, and for example, carbon fibers, boron fibers, silicon carbide fibers, glass fibers, or aramid fibers are preferable, and carbon fibers are more preferable.
  • the type of carbon fibers for example, any of a PAN type and a pitch type can be used, and these can be used alone or in combination according to the purpose or application.
  • a bonding resin (the matrix resin 106 for the bonding resin layer 103A) constituting the bonding resin layers 103 and 103A which adhere the metal member 101 and the FRP layer 102 of the metal-FRP composite bodies 100 and 200 is a solidified product of a phenoxy resin (A) alone or a cured product of a bonding resin composition containing 50 parts by weight or more of a phenoxy resin (A) in 100 parts by weight of resin components. In this manner, the metal member 101 and the FRP layer 102 can be firmly adhered using the phenoxy resin (A) or the bonding resin composition.
  • the bonding resin composition preferably contains 55 parts by weight or more of the phenoxy resin (A) in 100 parts by weight of resin components. Examples of the form of the phenoxy resin (A) or the bonding resin composition include a powder, a liquid such as a varnish and a solid such as a film.
  • the "phenoxy resin” is a linear polymer obtained according to a condensation reaction of a dihydric phenolic compound and epihalohydrin or a poly addition reaction of a dihydric phenolic compound and a bifunctional epoxy resin and is an amorphous thermoplastic resin.
  • the phenoxy resin (A) can be obtained by a conventionally known method in a solution or with no solvent, and can be used in any form of a varnish, a film, and a powder.
  • the mass average molecular weight (Mw) is, for example, in a range of 10,000 to 200,000, preferably in a range of 20,000 to 100,000, and more preferably in a range of 30,000 to 80,000.
  • the Mw is a value that is measured through gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
  • the hydroxyl equivalent (g/eq) of the phenoxy resin (A) used in the present invention is, for example, in a range of 50 to 1,000, preferably in a range of 50 to 750, and particularly preferably in a range of 50 to 500.
  • the hydroxyl equivalent of the phenoxy resin (A) is too low, since the number of hydroxyl groups increases, and thus the water absorption rate increases, there is a concern of mechanical properties of the cured product deteriorating.
  • the hydroxyl equivalent of the phenoxy resin (A) is too high, since the number of hydroxyl groups decreases and the affinity with an adherend decreases, there is a risk of mechanical properties of the metal-FRP composite bodies 100 and 200 deteriorating.
  • the glass transition temperature (Tg) of the phenoxy resin (A) is, for example, suitable in a range of 65 °C to 150 °C, and preferably in a range of 70 °C to 150 °C.
  • Tg is lower than 65 °C, the moldability is improved, but since the fluidity of the resin is too high, it is difficult to secure the thickness of the bonding resin layers 103 and 103A.
  • Tg is higher than 150 °C, since the melt viscosity tends to increase, it is difficult to impregnate it into a reinforced fiber base material without defects such as voids, and an adhering process at a higher temperature is required.
  • Tg of the phenoxy resin (A) is a numerical value that is measured using a differential scanning calorimeter under heating conditions of 10 °C/min and in a temperature range of 20 to 280 °C and calculated from a peak value of a second scan.
  • the phenoxy resin (A) is not particularly limited as long as the above physical properties are provided, and preferable examples thereof include bisphenol A type phenoxy resins (for example, Pheno Tohto YP-50, Pheno Tohto YP-50S, and Pheno Tohto YP-55U commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol F type phenoxy resins (for example, Pheno Tohto FX-316 commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), copolymer type phenoxy resins of bisphenol A and bisphenol F (for example, YP-70 commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), and special phenoxy resins such as brominated phenoxy resins, phosphorus-containing phenoxy resins, and sulfone group-containing phenoxy resins other than the above examples (for example, Pheno Tohto YPB-43C, Phen
  • the bonding resin composition can contain a thermoplastic resin and a thermosetting resin other than the phenoxy resin (A).
  • the type of the thermoplastic resin is not particularly limited, and, for example, at least one selected from thermoplastic aromatic polyesters such as a polyolefin and its acid-modified products, polystyrene, polymethyl methacrylate, an AS resin, an ABS resin, polyethylene terephthalate, and polybutylene terephthalate, and a polycarbonate, polyimide, polyamide, polyamideimide, polyether imide, polyether sulfone, polyphenylene ether and its modified products, polyphenylene sulfide, polyoxymethylene, polyarylate, polyether ketone, polyether ether ketone, polyether ketone ketone, thermoplastic epoxy, and the like can be used.
  • the thermosetting resin for example, at least one selected from among an epoxy resin, a vinyl ester resin, a phenol resin, a urethane resin, and the like
  • the bonding resin (composition) preferably has a melt viscosity of 3,000 Pa ⁇ s or less, more preferably has a melt viscosity in a range of 90 to 2,900 Pa ⁇ s, and most preferably has a melt viscosity in a range of 100 to 2,800 Pa ⁇ s.
  • the melt viscosity in a temperature range of 160 to 250 °C exceeds 3,000 Pa ⁇ s, the fluidity during melting deteriorates, and defects such as voids are easily generated in the bonding resin layers 103 and 103A.
  • a crosslinking agent for example, an acid anhydride, an isocyanate, a caprolactam, or the like
  • a crosslinkable bonding resin composition using secondary hydroxyl groups contained in the phenoxy resin (A) can be obtained.
  • the crosslinking reaction since the heat resistance, which was a drawback of the phenoxy resin, can be improved, application to members that are used in a higher temperature environment is possible.
  • a crosslinkable bonding resin composition in which an epoxy resin (B) and a crosslinking agent (C) are added is preferably used.
  • Tg of the cross-linked cured product of the crosslinkable bonding resin composition is, for example, 160 °C or higher, and preferably in a range of 170 to 220 °C.
  • a bifunctional or higher epoxy resin is preferable.
  • the bifunctional or higher epoxy resin include bisphenol A type epoxy resins (for example, Epototo YD-011, Epototo YD-7011, and Epototo YD-900 commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol F type epoxy resins (for example, Epototo YDF-2001 commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), diphenyl ether type epoxy resins (for example, YSLV-80DE commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), tetramethyl bisphenol F type epoxy resins (for example, YSLV-80XY commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol sulfide type epoxy resins (for example, YSLV-
  • the epoxy resin (B) is not particularly limited, but a crystalline epoxy resin is preferable and a crystalline epoxy resin having a melting point in a range of 70 °C to 145 °C and a melt viscosity of 2.0 Pa ⁇ s or less at 150 °C is more preferable.
  • a crystalline epoxy resin exhibiting such melting properties it is possible to reduce the melt viscosity of the crosslinkable bonding resin composition as the bonding resin composition and it is possible to improve the bondability.
  • the melt viscosity exceeds 2.0 Pa ⁇ s, the moldability of the crosslinkable bonding resin composition may be reduced and the homogeneity of the metal-FRP composite bodies 100 and 200 may deteriorate.
  • crystalline epoxy resin examples include Epototo YSLV-80XY, YSLV-70XY, YSLV-120TE, and YDC-1312 (commercially available from Nippon Steel & Sumikin Chemical Co., Ltd.),YX-4000, YX-4000H, YX-8800, YL-6121H, YL-6640, and the like (commercially available from Mitsubishi Chemical Corporation), HP-4032, HP-4032D, HP-4700, and the like (commercially available from DIC Corporation), and NC-3000 and the like (commercially available from Nippon Kayaku Co., Ltd.).
  • the crosslinking agent (C) forms an ester bond with secondary hydroxyl groups in the phenoxy resin (A) and thus causes the phenoxy resin (A) to be three-dimensionally crosslinked. Therefore, unlike strong crosslinking such as curing of the thermosetting resin, since crosslinking can be released due to a hydrolysis reaction, the metal member 101 and the FRP layer 102 can be easily peeled off from each other. Accordingly, it is possible to recycle the metal member 101 and the FRP layer 102.
  • an acid anhydride is preferable.
  • the acid anhydride is not particularly limited as long as it is a solid at room temperature and does not exhibit much sublimation.
  • an aromatic acid dianhydride having two or more acid anhydride groups that react with hydroxyl groups in the phenoxy resin (A) is preferable.
  • an aromatic compound having two acid anhydride groups such as pyromellitic anhydride is preferably used because it has a higher crosslinking density than a trimellitic anhydride with respect to hydroxyl groups, and the heat resistance is improved.
  • aromatic acid dianhydrides for example, an aromatic acid dianhydride having compatibility with respect to the phenoxy resin (A) and the epoxy resin (B) such as 4,4'-oxydiphthalic acid, ethylene glycol bisanhydro trimellitate, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride is more preferable because it has a stronger effect of improving Tg.
  • an aromatic tetracarboxylic acid dianhydride having two acid anhydride groups such as pyromellitic anhydride is preferably used because it has an improved crosslinking density and improved heat resistance compared with those of phthalic anhydride having only one acid anhydride group.
  • the aromatic tetracarboxylic acid dianhydride has favorable reactivity because it has two acid anhydride groups, whereby a cross-linked cured product with a strength sufficient for demolding is obtained in a short molding time, and it is possible to increase the final crosslinking density in order for four carboxyl groups to be generated due to an esterification reaction with secondary hydroxyl groups in the phenoxy resin (A).
  • crosslinking and curing occur due to an esterification reaction between secondary hydroxyl groups in the phenoxy resin (A) and an acid anhydride group in the crosslinking agent (C), and moreover, a reaction between a carboxyl group generated due to the esterification reaction and an epoxy group in the epoxy resin (B).
  • a phenoxy resin crosslinked component can be obtained due to the reaction between the phenoxy resin (A) and the crosslinking agent (C).
  • melt viscosity of the bonding resin composition can be reduced due to coexistence of the epoxy resin (B), excellent characteristics such as improvement in impregnation with an adherend, promotion of a crosslinking reaction, improvement in the crosslinking density, and improvement in the mechanical strength are exhibited.
  • the crosslinkable bonding resin composition also include the epoxy resin (B), but the phenoxy resin (A) which is a thermoplastic resin is a main component, and an esterification reaction between its secondary hydroxyl groups and an acid anhydride group in the crosslinking agent (C) is preferential. That is, since some time is taken for a reaction between an acid anhydride used as the crosslinking agent (C) and the epoxy resin (B), a reaction between the crosslinking agent (C) and secondary hydroxyl groups in the phenoxy resin (A) occurs first.
  • a cross-linked cured product obtained using the crosslinkable bonding resin composition retains its property of being a thermoplastic resin due to its crosslinked curing mechanism, and also has a better storage stability than an epoxy resin composition in which an acid anhydride is used as a curing agent.
  • the epoxy resin (B) is preferably added in a range of 5 to 85 parts by weight.
  • An amount of the epoxy resin (B) added with respect to 100 parts by weight of the phenoxy resin (A) is more preferably in a range of 9 to 83 parts by weight and most preferably in a range of 10 to 80 parts by weight.
  • an amount of the epoxy resin (B) added is less than 5 parts by weight, this is not preferable because an effect of improving the crosslinking density due to addition of the epoxy resin (B) cannot be obtained, the cross-linked cured product of the crosslinkable bonding resin composition is less likely to exhibit a Tg of 160 °C or higher, and the fluidity deteriorates.
  • An amount of the crosslinking agent (C) added is generally in a range of 0.6 to 1.3 mol of acid anhydride groups with respect to 1 mol of secondary hydroxyl groups of the phenoxy resin (A), and is preferably in a range of 0.7 to 1.3 mol, and more preferably in a range of 1.1 to 1.3 mol thereof.
  • an amount of acid anhydride groups is too small, since the crosslinking density is low, the mechanical properties and heat resistance deteriorate, and when an amount thereof is too large, unreacted acid anhydride and carboxyl groups adversely affect curing characteristics and the crosslinking density. Therefore, it is preferable to adjust an amount of the epoxy resin (B) added according to an amount of the crosslinking agent (C) added.
  • an amount of the epoxy resin (B) added may be set to be in a range of 0.5 to 1.2 mol in terms of an equivalent proportion with respect to the crosslinking agent (C).
  • an equivalent proportion of the crosslinking agent (C) with respect to the epoxy resin (B) is in a range of 0.7 to 1.0 mol.
  • an amount of the crosslinking agent (C) added is converted to parts by weight, although it depends on the type of crosslinking agent which is used, it is 20 to 100 parts by weight, preferably 30 to 100 parts by weight, and most preferably 40 to 100 parts by weight with respect to 100 parts by weight of the phenoxy resin.
  • crosslinking agent (C) When the crosslinking agent (C) is added together with the phenoxy resin (A) and the epoxy resin (B), it is possible to obtain a crosslinkable bonding resin composition, and a promoter (D) as a catalyst may be additionally added so that the crosslinking reaction reliably occurs.
  • the promoter (D) is not particularly limited as long as it is a solid at room temperature and exhibits little sublimation, and examples thereof include tertiary amines such as triethylenediamine, imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate.
  • tertiary amines such as triethylenediamine
  • imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole
  • organic phosphines such as triphenylphosphine
  • tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate.
  • Such promoters (D)
  • an imidazole-based latent catalyst which has a catalyst activation temperature of 130 °C or higher and which is a solid at room temperature is preferably used as the promoter (D).
  • an amount of the promoter (D) added is preferably in a range of 0.1 to 5 parts by weight with respect to a total amount of 100 parts by weight of the phenoxy resin (A), the epoxy resin (B), and the crosslinking agent (C).
  • the crosslinkable bonding resin composition is a solid at room temperature.
  • the lowest melt viscosity which is a lower limit value of a melt viscosity in a temperature range of 160 to 250 °C, is preferably 3,000 Pa ⁇ s or less, more preferably 2,900 Pa ⁇ s or less, and most preferably 2,800 Pa ⁇ s or less.
  • additives for example, natural rubber, synthetic rubber, an elastomer, various inorganic fillers, solvents, extender pigments, colorants, antioxidants, UV inhibitors, flame retardants, and flame retardant aids, can be added to the above bonding resin composition (including a crosslinkable bonding resin composition) as long as its bondability and physical properties are not impaired.
  • a reinforced fiber base material which becomes the reinforced-fiber material 105 for example, a non-woven fabric base material using chopped fibers, a cloth material using continuous fibers, a unidirectional reinforced fiber base material (UD material), and the like can be used, and in consideration of a reinforcing effect, it is preferable to use a cloth material or a UD material.
  • thermosetting resins such as an epoxy resin and a vinyl ester resin
  • thermoplastic aromatic polyesters such as a phenoxy resin, a polyolefin, and acid-modified products thereof, polyethylene terephthalate and polybutylene terephthalate
  • thermoplastic resins such as a polycarbonate, polyimide, polyamide, polyamideimide, polyether imide, polyether sulfone, polyphenylene ether and modified products thereof, polyarylate, polyether ketone, polyether ether ketone, and polyether ketone ketone can be used, and it is preferable to form the matrix resin 104 using a resin composition exhibiting favorable bondability with the phenoxy resin (A).
  • examples of a resin exhibiting favorable bondability with the phenoxy resin (A) include an epoxy resin, a phenoxy resin, a polyolefin resin that is acid-modified with maleic anhydride or the like, and a polycarbonate, polyarylate, polyimide, polyamide, and polyether sulfone.
  • these resins those having low bondability with respect to the metal member 101 are included, but they can be indirectly adhered to the metal member 101 with the bonding resin layers 103 and 103A therebetween.
  • the matrix resin 104 it is more preferable to form the matrix resin 104 using the same resin or the same type of resin as the resin constituting the bonding resin layers 103 and 103A (the matrix resin 106 for the bonding resin layer 103A).
  • the shear strength between the metal member 101 and the fiber-reinforced resin material including the FRP layer 102 and the bonding resin layers 103 and 103A is preferably 40 N/5 mm or more and more preferably 45 N/5 mm or more. Most preferably, the shear strength is 50 to 1,500 N/5 mm. When the shear strength is less than 40 N/5 mm, the mechanical strength of the metal-FRP composite bodies 100 and 200 may be insufficient and excellent durability may not be obtained.
  • peeling off of the metal member 101 from the metal-FRP composite bodies 100 and 200 is preferably cohesive peeling off and it is more preferable that peeling off not occur.
  • peeling surface of the peeled metal member 101 is observed, it is possible to distinguish cohesive peeling and interfacial peeling.
  • a bonding part be cohesively peeled off rather than interfacially peeled off. The reason for this is that, in the case of interfacial peeling off, there is vulnerability to a thermal cycle, an adhesive force is uneven, it is difficult to manage the quality, and defective products are easily generated.
  • the metal-FRP composite body 100 is obtained by bonding a FRP (or an FRP molding prepreg as its precursor) processed into a desired shape which becomes the FRP layer 102 and the metal member 101 with the phenoxy resin (A) or a bonding resin composition which becomes the bonding resin layer 103 and solidifying the phenoxy resin (A) or curing the bonding resin composition.
  • a FRP or an FRP molding prepreg as its precursor
  • thermocompression A method in which a coating film (which becomes the bonding resin layer 103) formed of the phenoxy resin (A) or the bonding resin composition is formed on the surface of the metal member 101 and an FRP or an FRP molding prepreg (first prepreg) which becomes the FRP layer 102 is then laminated and subjected to thermocompression
  • a powdered or liquid phenoxy resin (A) or a bonding resin composition is applied to at least one side surface of the metal member 101 to form a coating film 110.
  • the coating film 110 may be formed on the side of an FRP or an FRP molding prepreg 111 (first prepreg) which becomes the FRP layer 102 rather than on the side of the metal member 101.
  • first prepreg an FRP molding prepreg 111
  • the FRP molding prepreg 111 which becomes the FRP layer 102 is disposed in an overlapping manner on the side on which the coating film 110 is formed, and the metal member 101, the coating film 110, and the FRP molding prepreg 111 are laminated in this order to form a laminate.
  • the FRP can be laminated in place of the FRP molding prepreg 111.
  • a bonding surface of the FRP is preferably roughened by, for example, blast processing, or activated by a plasma treatment, a corona treatment or the like.
  • this laminate is heated or pressurized, as shown in FIG. 5(c) , the metal-FRP composite body 100 can be obtained.
  • the method A regarding a method for forming the coating film 110 which becomes the bonding resin layer 103, a method for applying powder of the phenoxy resin (A) or the bonding resin composition to the surface of the metal member 101 is preferable.
  • the phenoxy resin (A) or the bonding resin composition has a form of fine particles and is easily melted, and voids escape easily because appropriate voids are maintained in the coating film 110.
  • the FRP or the FRP molding prepreg 111 is subjected to thermocompression, since the phenoxy resin (A) or the bonding resin composition favorably wets the surface of the metal member 101, a degassing process such as varnish coating is not necessary, and defects due to insufficient wettability such as generation of voids as seen in the film are unlikely to occur.
  • the coating film 110 is formed on both surfaces of the metal member 101, and in FIG. 5(b) , the FRP molding prepreg 111 (or the FRP) may be laminated on each of both sides of the coating film 110.
  • the FRP molding prepreg 111 (or the FRP) which becomes the FRP layer 102 is not limited to one layer, and may be formed into a plurality of layers (refer to FIG. 2 ).
  • the FRP molding prepreg 111 (or the FRP) which becomes the FRP layer 102 is interposed in a sandwich form using two or more metal members 101 for lamination.
  • the FRP can be laminated in place of the FRP molding prepreg 111.
  • a bonding surface of the FRP is preferably roughened by, for example, blast processing, or activated by a plasma treatment, a corona treatment or the like.
  • the bonding sheet 110A and the FRP molding prepreg 111 may be laminated on both surfaces of the metal member 101.
  • the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) is not limited to one layer, and may be formed into a plurality of layers (refer to FIG. 2 ).
  • the bonding sheet 110A and the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) are interposed in a sandwich form using two or more metal members 101 for lamination.
  • the metal-FRP composite body 200 is obtained by bonding an FRP (or the FRP molding prepreg 111) which becomes the FRP layer 102 and the metal member 101 which are processed into a desired shape with a bonding sheet (which becomes the bonding resin layer 103A) containing the phenoxy resin (A) or the bonding resin composition and the reinforced-fiber material 107 and solidifying the phenoxy resin (A) or curing the bonding resin composition.
  • a bonding sheet which becomes the bonding resin layer 103A
  • the bonding sheet which becomes the bonding resin layer 103A
  • the phenoxy resin (A) or the bonding resin composition and the reinforced-fiber material 107 solidifying the phenoxy resin (A) or curing the bonding resin composition.
  • a bonding sheet 110B containing the phenoxy resin (A) or the bonding resin composition and the reinforced-fiber material 107 and the FRP molding prepreg 111 which becomes the FRP layer 102 are disposed in an overlapping manner on at least one side surface of the metal member 101, and the metal member 101, the bonding sheet 110B, and the FRP molding prepreg 111 are laminated in this order to form a laminate.
  • the bonding sheet 110B is a sheet-like prepreg for bonding the metal member 101 and the FRP layer 102.
  • the FRP can be laminated in place of the FRP molding prepreg 111.
  • a bonding surface of the FRP is preferably roughened by, for example, blast processing, or activated by a plasma treatment, a corona treatment or the like.
  • the FRP molding prepreg 111 (or the FRP) is adhered to the metal member 101 using the bonding sheet 110B containing the reinforced-fiber material 107.
  • a resin component (a component as the matrix resin 106) derived from the phenoxy resin (A) or the bonding resin composition impregnated with the reinforced-fiber material 107 functions as a bonding resin.
  • the bonding sheet 110B and the FRP molding prepreg 111 may be laminated on both surfaces of the metal member 101.
  • the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) is not limited to one layer, and may be formed into a plurality of layers (refer to FIG. 4 ).
  • the bonding sheet 110B and the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) are interposed in a sandwich form using two or more metal members 101 for lamination.
  • Combination of the metal member 101 and the FRP is preferably performed, for example, as follows.
  • thermocompression conditions in which the metal member 101, the bonding sheet 110A or 110B, and the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) are combined are as follows.
  • thermocompression temperature is not particularly limited, but it is, for example, in a range of 100 °C to 400 °C, and preferably in a range of 150 to 300 °C, more preferably in a range of 160 °C to 270 °C and most preferably in a range of 180 °C to 250 °C.
  • a temperature equal to or higher than a melting point is more preferable for a crystalline resin and a temperature equal to or higher than Tg+150 °C is more preferable for a non-crystalline resin.
  • the pressure during compression is, for example, preferably 3 MPa or higher and more preferably in a range of 3 to 5 MPa.
  • the pressure exceeds an upper limit, since an excess pressure is applied, deformation or damage can be caused, and when the pressure is lower than a lower limit, impregnation into the reinforced fiber base material deteriorates.
  • thermocompression can be performed, and a range of 5 to 20 minutes is preferable.
  • combinatory batch molding of the metal member 101, the bonding sheet 110A or 110B, and the FRP molding prepreg 111 which becomes the FRP layer 102 (or the FRP) may be performed using a press molding device.
  • Combinatory batch molding is preferably performed by hot pressing, but it is possible to perform processing by quickly setting a material preheated to a predetermined temperature in advance in a press molding device at a low temperature.
  • crosslinkable bonding resin composition when used, in the thermocompression process, a cured product in a first cured state which is solidified but it is not crosslinked after the phenoxy resin and the like contained in the crosslinkable bonding resin composition are melted can be used to form the bonding resin layers 103 and 103A.
  • the same as or the same type of crosslinkable bonding resin composition is used for a matrix resin of the FRP molding prepreg 111 which becomes the FRP layer 102, the FRP layer 102 containing the matrix resin 104 formed of a cured product in a first cured state can be formed.
  • the thermocompression process it is possible to produce an intermediate (preform) of the metal-FRP composite bodies 100 and 200 in which the metal member 101, the bonding resin layers 103 and 103A formed of a cured product in a first cured state, and the FRP layer 102 are laminated and integrated, and, for example, it can be applied to prevent positional deviation between them when the metal member 101 and the FRP layer 102 are collectively molded and combined.
  • the matrix resin 104 that is a cured product in a first cured state may be used.
  • the intermediate when the intermediate is subjected to the thermocompression process and then additionally subjected to a process with additional heat, at least the resin of the bonding resin layers 103 and 103A formed of a cured product in a first cured state can be crosslinked and cured so that it can be changed to a cross-linked cured product in a second cured state.
  • the matrix resin 104 formed of a cured product in a first cured state can be crosslinked and cured so that it can be changed to a cross-linked cured product in a second cured state.
  • the temperature in the thermocompression process for obtaining a cured product in a first cured state is lower than 160 °C, and preferably 120 to 150 °C, and the pressure is 1 MPa or higher, and preferably 1 to 5 MPa.
  • the additional heating process for changing a cured product in a first cured state to a cured product in a second cured state is preferably performed, for example, in a temperature range of 160 to 250 °C and for a time of about 10 to 30 minutes.
  • a pressure of 3 MPa or higher can be applied.
  • post curing is preferably performed on the metal-FRP composite bodies 100 and 200 after thermocompression, for example, in a temperature range of 200 to 250 °C for about 30 to 60 minutes. It is also possible to use thermal history in the post process such as coating for post curing.
  • Tg after crosslinking and curing is greatly improved compared to the phenoxy resin (A) alone. Therefore, before and after the additional heating process is performed on the intermediate (that is, a process in which the resin changes from a cured product in a first cured state to a cross-linked cured product in a second cured state), Tg changes.
  • Tg of the resin before crosslinking in the intermediate is, for example, 150 °C or lower, and on the other hand, since Tg of the resin crosslinked after the additional heating process is improved in the range of, for example, 160 °C or higher, and preferably 170 to 220 °C, it is possible to significantly improve the heat resistance.
  • the reinforced fiber base material which becomes the reinforced-fiber material 107 as in the FRP layer 102, for example, a non-woven fabric base material using chopped fibers, a cloth material using continuous fibers, a unidirectional reinforced fiber base material (UD material), or the like can be used, and in consideration of a reinforcing effect, a cloth material or a UD material is preferably used.
  • a prepreg produced using a powder coating method is more preferably used than a prepreg produced by a conventionally known method such as wet melting and a film stack method.
  • the prepreg produced by a powder coating method has favorable drapability because the resin in a fine particle state is impregnated into the reinforced fiber base material, and is suitable for batch molding, heating and pressing because it can conform to an adherend even if it has a complex shape.
  • an electrostatic painting method, a fluidized bed method, or a suspension method is a main method.
  • the electrostatic painting method and the fluidized bed method are methods suitable for a thermoplastic resin, and are preferable because the process is simple and the productivity is favorable, and particularly, the electrostatic painting method is the most suitable method because the uniformity of attachment of the phenoxy resin (A) or bonding resin composition to the reinforced fiber base material is favorable.
  • the bonding sheet 110B When the bonding sheet 110B is formed, if powder coating of the phenoxy resin (A) or the bonding resin composition (which becomes the matrix resin 106) containing the phenoxy resin (A) is performed, it is preferable to obtain a prepreg by forming the phenoxy resin (A) or the bonding resin composition into a predetermined fine powder and attaching the fine powder to a reinforced fiber base material by powder coating.
  • a grinding and mixing machine such as a dry grinding machine at a low temperature (century dry mill) is suitably used, and the present invention is not limited thereto.
  • a grinding and mixing machine such as a dry grinding machine at a low temperature (century dry mill) is suitably used, and the present invention is not limited thereto.
  • respective components may be pulverized and then mixed, or respective components may be mixed in advance and then pulverized.
  • pulverizing conditions may be set so that each fine powder has an average particle size to be described below.
  • the fine powder obtained in this manner has an average particle size that is in a range of 10 to 100 ⁇ m, preferably in a range of 40 to 80 ⁇ m, and more preferably in a range of 40 to 50 ⁇ m.
  • the average particle size exceeds 100 ⁇ m, in powder coating in an electrostatic field, the energy when the phenoxy resin (A) or the bonding resin composition collides with a fiber increases, and an attachment rate for the reinforced fiber base material decreases.
  • the average particle size is less than 10 ⁇ m, particles are scattered due to an associated air flow and the attachment efficiency is lowered, and resin fine powder suspended in the air can cause deterioration in a working environment.
  • the average particle size of fine powder of the phenoxy resin (A) and fine powder of the epoxy resin (B) is preferably in a range of 1 to 1.5 times the average particle size of fine powder of the crosslinking agent (C).
  • the crosslinking agent (C) When the particle size of the fine powder of the crosslinking agent (C) is made finer than the particle size of fine powder of the phenoxy resin (A) and the epoxy resin (B), the crosslinking agent (C) enters and is attached to the inside of the reinforced fiber base material, and the crosslinking agent (C) is uniformly present around particles of the phenoxy resin (A) and particles of the epoxy resin (B), and thus the crosslinking reaction can reliably proceed.
  • an amount of the phenoxy resin (A) or the bonding resin composition (which becomes the matrix resin 106) attached to the reinforced fiber base material is, for example, preferably in a range of 20 to 50%, more preferably in a range of 25 to 45%, and most preferably in a range of 25 to 40%.
  • RC exceeds 50%, mechanical properties such as a tensile and flexural modulus of FRP deteriorate, and when RC is less than 20%, an amount of the resin attached is very small so that impregnation of the matrix resin 106 into the reinforced fiber base material is insufficient and there is a concern of thermophysical properties and mechanical properties deteriorating.
  • the fine powder of the powder-coated phenoxy resin (A) or bonding resin composition (which becomes the matrix resin 106) is fixed to the reinforced fiber base material by heat melting.
  • powder coating may be performed on the reinforced fiber base material and then heated and fused, or powder coating may be performed on the reinforced fiber base material heated in advance and thus fusion may be performed simultaneously with application of fine powder of the phenoxy resin (A) or the bonding resin composition to the reinforced fiber base material.
  • incomplete melting does not mean melting so that all of a fine powder 108 of the raw material resin is made into droplets and flows, but refers to a state in which some of the fine powder 108 is completely made into droplets, but in most of the fine powder 108, only the surface is melted and made into a liquid and center parts remain in a solid state.
  • the phenoxy resin (A) or the bonding resin composition which becomes the matrix resin 106 is concentrated on the surface of the reinforced fiber base material, and does not enter the inside of the reinforced fiber base material like a molded article after heating, pressurizing, and molding.
  • a heating time required for forming a partially fused structure of the phenoxy resin (A) or the bonding resin composition after powder coating is not particularly limited, and generally 1 to 2 minutes is suitable.
  • the melting temperature is in a range of 150 to 240 °C, preferably in a range of 160 to 220 °C, and more preferably in a range of 180 to 200 °C.
  • the cure reaction may proceed, and when the melting temperature is lower than a lower limit, heat fusion is insufficient, and during a handling operation, there is a concern of fine powder of the phenoxy resin (A) or the bonding resin composition dropping off and falling off.
  • a method for producing the bonding sheet 110B by a powder coating method will be described in further detail with reference to FIG. 8 and FIG. 9 .
  • a case in which the bonding sheet 110B in which a partially fused structure 108A of the phenoxy resin (A) or the bonding resin composition (hereinafter collectively referred to as a "raw material resin") is formed on both surfaces of the reinforced fiber base material will be exemplified.
  • the following method A1 or method A2 can be performed.
  • the method A1 can include the following process a and process b.
  • a fine powder 108 of a raw material resin which is a solid at room temperature is attached to at least one side surface of a sheet-like reinforced fiber base material formed of the reinforced-fiber material 107 by a powder coating method and thus a resin-attached fiber base material 107A is formed.
  • the powder coating method since the raw material resin composition is fine particles and is easily melted, and appropriate voids are retained in the coating film after coating, it becomes an air flow path and voids are unlikely to be generated.
  • the bonding sheet 110B and the metal member 101 are subjected to thermocompression, first, the resin melted on the surface of the prepreg is quickly wet and spreads on the surface of the metal member 101 and then impregnated into the reinforced fiber base material. Therefore, compared to a melt impregnation method of the related art, defects due to insufficient wettability of the resin melted on the surface of the metal member 101 are less likely to occur. That is, in a melt impregnation method for binding the metal member 101 using the resin extruded from the reinforced fiber base material, in the produced prepreg, wettability of the resin melted on the surface of the metal member 101 tends to be insufficient. However, this problem can be avoided in the powder coating method. A preferable type of the powder coating method, coating conditions, the resin proportion (RC), and the like are as described above.
  • FIG. 8(b) shows a state in which the fine powder 108 of the raw material resin is attached to both side surfaces of the resin-attached fiber base material 107A, but the fine powder 108 may be attached to only one side surface of the resin-attached fiber base material 107A.
  • the resin-attached fiber base material 107A is subjected to a heat treatment and the fine powder 108 of the raw material resin is incompletely melted and then solidified, and thus the bonding sheet 110B which is a prepreg having the partially fused structure 108A formed of the raw material resin is formed.
  • the partially fused structure 108A in the vicinity of the surface layer part of the reinforced fiber base material, the fine powder 108 is partially melted due to a heat treatment, and a molten material of the adjacent fine powder 108 is fused and solidified in a mesh-like linked state.
  • the partially fused structure 108A adhesion to the reinforced fiber base material is improved and it is possible to prevent the fine powder 108 from falling off, and a certain air permeability in the thickness direction of the reinforced fiber base material is secured. Therefore, in a heat and press treatment in which the metal member 101 is subjected to thermocompression, an air flow path in the reinforced fiber base material is secured and generation of voids can be avoided.
  • the partially fused structure 108A is uniformly formed on the entire surface of the bonding sheet 110B, and may be unevenly distributed microscopically.
  • FIG. 8(c) shows a state in which the partially fused structure 108A is formed on both side surfaces of the bonding sheet 110B, but the partially fused structure 108A may be formed only one side surface of the bonding sheet 110B.
  • the heat treatment is preferably performed in a temperature range of about 100 °C to 400 °C, and a temperature equal to or lower than the melting point is more preferable when the raw material resin is a crystalline resin, and a temperature equal to or lower than Tg+150 °C is more preferable when the raw material resin is a non-crystalline resin.
  • the heat treatment exceeds an upper limit, thermal melting of the fine powder 108 goes too far, the partially fused structure 108A is not formed, and air permeability can be impaired.
  • the partially fused structure 108A is not formed, heat fusion to the reinforced fiber base material is insufficient, and during a handling operation of the bonding sheet 110B, there is a concern of the fine powder 108 from dropping off and falling off.
  • the heat treatment time is not particularly limited as long as the fine powder 108 of the raw material resin attached to the reinforced fiber base material can be fixed to the reinforced fiber base material, and for example, 1 to 5 minutes is suitable. That is, when the heat treatment is performed for a much shorter time than molding, the resin of the partially fused structure 108A can be fixed to the reinforced fiber base material, and it is possible to prevent powder from falling off.
  • the raw material resin (the partially fused structure 108A and the fine powder 108 without change) is concentrated in the vicinity of the surface of the reinforced fiber base material and does not enter the inside of the reinforced fiber base material like a molded article after heating and pressurizing.
  • the heat treatment may be performed when the resin-attached fiber base material 107A is in contact with the metal member 101.
  • the thickness of the bonding sheet 110B is preferably in a range of 40 to 200 ⁇ m and more preferably in a range of 50 to 150 ⁇ m.
  • the thickness of the bonding sheet 110B is less than 40 ⁇ m, impregnation failure may occur due to deterioration of handling properties and an insufficient resin.
  • the thickness of the bonding sheet 110B exceeds 200 ⁇ m, impregnation of the melted resin into the reinforced fiber base material after heating and pressurizing is insufficient, which can lead a decrease in the mechanical strength.
  • the air permeability in the thickness direction is preferably in a range of 500 to 1,000 cc/cm 2 /sec and more preferably in a range of 700 to 900 cc/cm 2 /sec.
  • the air permeability is less than 500 cc/cm 2 /sec, in a heat and press treatment in which the metal member 101 is subjected to thermocompression, an air flow path in the bonding sheet 110B decreases and voids are easily generated.
  • the surface roughness is preferably an arithmetic average roughness (Ra) of 0.010 to 0.100 mm and more preferably 0.015 to 0.075 mm.
  • Ra arithmetic average roughness
  • the bonding sheet 110B is interposed between the dense metal members 101, the bonding sheet 110B and the metal member 101 are firmly bonded, and the metal-FRP composite body 200 having an excellent mechanical strength is obtained.
  • Ra is less than 0.010 mm, since the bonding sheet 110B and other prepregs are easily fused in the heat and press treatment, there is no air flow path, which causes generations of voids. On the other hand, when Ra exceeds 0.100 mm, it is not suitable because voids remain.
  • the bonding sheet 110B in which the partially fused structure 108A formed of the raw material resin is formed based on the end surface of the original reinforced fiber base material, preferably 10 weight% or more and more preferably 10 to 40 weight% of the raw material resin within a range of 0 to 50% in the thickness direction is attached with respect to the thickness of the reinforced fiber base material.
  • a gradient is provided in an attachment concentration of the raw material resin, when a surface of the bonding sheet 110B on which the partially fused structure 108A is formed is brought into contact with the metal member 101 and heated and pressurized, the sufficient melted resin can spread on the boundary between the bonding sheet 110B and the metal member 101.
  • the method A2 is a method in which the process a and the process b in the method A1 are collectively performed. That is, although not shown, the fine powder 108 of the raw material resin which is a solid at room temperature is attached to at least one side surface of the sheet-like reinforced fiber base material heated to a predetermined temperature by a powder coating method, the fine powder 108 is incompletely melted, and then solidified, and thus the bonding sheet 110B in which the partially fused structure 108A is formed is formed. In the method A1, the powder-coated fine powder 108 is fixed to the reinforced fiber base material according to the heat treatment. However, in the method A2, powder coating of the fine powder 108 is performed on the reinforced fiber base material heated in advance and thus fusion is performed simultaneously with application to the reinforced fiber base material to form the partially fused structure 108A.
  • FIG. 9 shows an example of a form in which the metal member 101, the bonding sheet 110B, and the FRP molding prepreg 111, which is a precursor of the FRP layer 102, are subjected to thermocompression.
  • the heat and press treatment is performed when a surface on which the partially fused structure 108A of the bonding sheet 110B is formed is brought into contact with at least a surface of the metal member 101, preferably a surface of the metal member 101 and a surface of the FRP molding prepreg 111, and thus the raw material resin attached to the bonding sheet 110B is completely melted and wet and spreads on the surface of the metal member 101, and at the same time, is impregnated into the reinforced fiber base material.
  • the raw material resin impregnated in this manner is cured to form the matrix resin 106 and the bonding resin layer 103A is formed, and thus the bonding resin layer 103A is firmly bonded to the metal member 101 and the FRP layer 102.
  • the partially fused structure 108A of the raw material resin in the bonding sheet 110B is brought into contact with the metal member 101 in the heat and press treatment and wet and spreads in a thin film form, the bondability between the bonding resin layer 103A and the metal member 101, and between the bonding resin layer 103A and the FRP layer 102 is improved, and the metal-FRP composite body 200 in which the FRP layer 102 and the metal member 101 are firmly bonded can be formed.
  • the raw material resin is completely melted due to heat and becomes a liquid, and penetrates into the bonding sheet 110B due to pressurizing. Since an air flow path is secured in the bonding sheet 110B having an air permeability that is controlled so that it has a predetermined level, the melted resin penetrates while expelling air, impregnation is completed in a short time even at a relatively low pressure, and generation of voids can be avoided.
  • thermocompression temperature can be appropriately set according to the melting point and Tg of the raw material resin to be used because the fine powder 108 of the raw material resin and the partially fused structure 108A are completely melted and impregnated into the entire reinforced fiber base material.
  • conditions in which the bonding sheet 110B is subjected to thermocompression with the metal member 101 are as described above.
  • the metal member 101, the bonding sheet 110B, and the FRP molding prepreg 111 may be molded and processed into an arbitrary three-dimensional shape.
  • the pressure at which the metal member 101, the bonding sheet 110B, and the FRP molding prepreg 111 are compressed and molded is preferably based on a pressure necessary for pressing and molding the metal member 101.
  • the bonding sheet 110B and the FRP molding prepreg 111 may be compressed on the metal member 101 molded into an arbitrary three-dimensional shape in advance.
  • Combinatory batch molding of the metal member 101 and the FRP layer 102 using a press molding device is preferably performed by hot pressing. However, it is possible to perform processing by quickly setting a material preheated to a predetermined temperature in advance in a press molding device at a low temperature.
  • the metal member 101, the bonding sheet 110B, and the FRP molding prepreg 111 may be temporarily fixed in advance. Temporary fixing conditions are not particularly limited as long as the partially fused structure 108A of the bonding sheet 110B is maintained and the air permeability is secured.
  • the FRP molding prepreg 111 used to form the FRP layer 102 for those adjacent to at least the bonding resin layers 103 and 103A, prepregs produced by the above powder coating method are preferably used.
  • the bonding resin layer 103A and the FRP molding prepreg 111 that are both produced by the powder coating method are used, and thus the two components are mixed together and integrated at a rough interface therebetween during thermocompression. Therefore, it is possible to improve the bonding strength between the bonding resin layer 103A and the FRP layer 102.
  • a particle size at which a cumulative volume was 50% based on the volume was measured using a laser diffraction and scattering type particle size distribution measuring device (Micro Trak MT3300EX, commercially available from Nikkiso Co., Ltd.).
  • a sample with a size of 4.3 cm 3 was interposed between parallel plates using a rheometer (commercially available from Anton Paar), while raising the temperature at 20 °C/min, the melt viscosity at 250 °C was measured under conditions of a frequency of 1 Hz and a load strain of 5%.
  • a minimum value of the viscosity at 160 °C to 250 °C was set as a melt viscosity.
  • a resin proportion was calculated from a weight (W1) of a reinforced fiber base material before the matrix resin was attached and a weight (W2) of an FRP molding material after the resin was attached using the following formula.
  • Resin proportion RC : % W 2 ⁇ W 1 / W 2 ⁇ 100
  • the metal-FRP composite body 100 was cut using a diamond cutter, and the obtained cross section was polished with abrasive paper and diamond abrasive grains, and then polished using a cross section polisher (CP) treatment, and observed under a scanning electron microscope (SEM), and thereby the thickness was measured.
  • CP cross section polisher
  • SEM scanning electron microscope
  • an FRP laminate was disposed on both sides of the metal member 101 with a thickness of t mm so that a total thickness (here, refers to a total thickness of the FRP layer 102 and the bonding resin layer 103 or 103A) was 0.4 mm, and subjected to thermocompression under conditions shown in examples and comparative examples, and thereby samples of a metal-FRP composite body for a bending test were obtained.
  • the white arrow in FIG. 10 indicates a load application direction.
  • two metal members 101 processed into a size of a thickness of t mm, a width of 5 mm and a length of 60 mm were prepared, and respective parts of 10 mm from ends of the metal members 101 were bonded to an FRP laminate formed to have a total thickness of 0.4 mm (here, refers to a total thickness of the FRP layer 102 and the bonding resin layer 103 or 103A), and thereby samples of a metal-FRP composite body for a shear test were produced. That is, the samples of a metal-FRP composite body for a shear test were produced by inserting an FRP laminate between vicinities of ends of two upper and lower metal members 101, and performing thermocompression under conditions shown in examples and comparative examples. Two white arrows in FIG. 11 indicate a tensile load application direction.
  • a powder obtained by pulverizing and classifying A-1 and having an average particle size D50 of 80 ⁇ m was used as the phenoxy resin (A), carbon fibers (UD material: Pyrofil TR50S 15L commercially available from Mitsubishi Rayon Co., Ltd.) that were opened and aligned in one direction were used as a base material, and in an electrostatic field, powder coating was performed under conditions of a charge of 70 kV and a spray air pressure of 0.32 MPa.
  • a powder obtained by pulverizing and classifying A-2 and having an average particle size D50 of 80 ⁇ m was used as the phenoxy resin (A), carbon fibers (UD material: Pyrofil TR50S 15L commercially available from Mitsubishi Rayon Co., Ltd.) that were opened and aligned in one direction were used as a reinforced fiber base material, and in an electrostatic field, powder coating was performed under conditions of a charge of 70 kV and a spray air pressure of 0.32 MPa.
  • A-1 100 parts by weight of A-1 as the phenoxy resin (A), 30 parts by weight of the epoxy resin (B), and 73 parts by weight of the crosslinking agent (C) were prepared and they were pulverized and classified to obtain a powder having an average particle size D50 of 80 ⁇ m, and dried and blended using a dry powder mixer (Rocking mixer commercially available from Aichi Electric Co., Ltd.).
  • crosslinkable phenoxy resin composition carbon fibers (UD material: Pyrofil TR50S 15L commercially available from Mitsubishi Rayon Co., Ltd.) that were opened and aligned in one direction were used as a reinforced fiber base material, and in an electrostatic field, powder coating was performed under conditions of a charge of 70 kV and a spray air pressure of 0.32 MPa. Then, heating and melting were performed in an oven at 170 °C for 1 minute, the resin was thermally fused to form a partially fused structure, and thereby a crosslinked phenoxy resin CFRP prepreg C having a thickness of 0.16 mm and a resin proportion (RC) of 48% was produced.
  • UD material Pyrofil TR50S 15L commercially available from Mitsubishi Rayon Co., Ltd.
  • the melt viscosity of the crosslinkable phenoxy resin composition at 250 °C was 250 Pa ⁇ s.
  • a plurality of produced prepregs were laminated and pressurized in a press machine heated to 200 °C at 3 MPa for 3 minutes to produce a CFRP laminate having a thickness of 2 mm, the laminate was post-cured at 170 °C for 30 minutes, and then cut into a test piece with a width of 10 mm and a length of 10 mm using a diamond cutter, and measurement was performed using a dynamic viscoelasticity measuring device (DMA 7e commercially available from Perkin Elmer) under heating conditions of 5 °C/min in a range of 25 to 250 °C, and the maximum peak of the obtained tan ⁇ was set as Tg.
  • DMA 7e dynamic viscoelasticity measuring device
  • a powder obtained by pulverizing and classifying A-1 and having an average particle size D50 of 80 ⁇ m was used as the phenoxy resin (A), and powder coating was performed under conditions of a charge of 70 kV and a spray air pressure of 0.32 MPa on an open fiber product (SA-3203 commercially available from Sakai Ovex Co., Ltd.) of a plain fabric reinforced fiber base material (cloth material: IMS60 commercially available from Toho Tenax Co., Ltd.) made of carbon fibers in an electrostatic field.
  • A-1 100 parts by weight of A-1 as the phenoxy resin (A), 30 parts by weight of the epoxy resin (B), and 73 parts by weight of the crosslinking agent (C) were prepared and they were pulverized and classified to obtain a powder having an average particle size D50 of 80 ⁇ m, and dried and blended using a dry powder mixer (Rocking mixer commercially available from Aichi Electric Co., Ltd.).
  • crosslinkable phenoxy resin composition powder coating was performed under conditions of a charge of 70 kV and a spray air pressure of 0.32 MPa on an open fiber product (SA-3203 commercially available from Sakai Ovex Co., Ltd.) of a plain fabric reinforced fiber base material (cloth material: IMS60 commercially available from Toho Tenax Co., Ltd.) made of carbon fibers in an electrostatic field. Then, heating and melting were performed in an oven at 170 °C for 1 minute, the resin was thermally fused to form a partially fused structure, and thereby a crosslinked phenoxy resin CFRP prepreg E having a thickness of 0.25 mm and a resin proportion (RC) of 48% was produced.
  • SA-3203 commercially available from Sakai Ovex Co., Ltd.
  • a plain fabric reinforced fiber base material cloth material: IMS60 commercially available from Toho Tenax Co., Ltd.
  • the temperature was lowered to 50 to 60 °C while continuing kneading, and then 5 parts by weight of dicyanamide as a curing agent, and 4 parts by weight of dimethyl urea as a curing promoter were added thereto and stirred so that they were uniformly dispersed and thereby an epoxy resin composition was obtained.
  • the viscosity of the epoxy resin composition measured using a cone plate viscometer at a predetermined temperature (90 °C) was 4 Pa ⁇ s
  • Tg of the cured product was 136 °C.
  • the epoxy resin composition was applied to a released PET film using a coater to produce an epoxy resin film having a thickness of 20 ⁇ m.
  • the resin film was superimposed on an open fiber product (SA-3203 commercially available from Sakai Ovex Co., Ltd.) of a plain fabric reinforced fiber base material (cloth material: IMS60 commercially available from Toho Tenax Co., Ltd.) made of carbon fibers from both surfaces, and heated and pressurized under conditions of a temperature of 95 °C and a pressure of 0.2 MPa, an epoxy resin composition for a carbon-fiber-reinforced composite material was impregnated, and thereby an epoxy resin CFRP prepreg K having a resin proportion (RC) of 48% and a thickness of 0.20 mm was produced.
  • SA-3203 commercially available from Sakai Ovex Co., Ltd.
  • a plain fabric reinforced fiber base material cloth material: IMS60 commercially available from Toho Tenax Co., Ltd.
  • A-1 was used as the phenoxy resin (A), a phenoxy resin was melted in an extruder heated to 200 to 230 °C, and a bonding resin sheet A having a thickness of 0.02 mm was produced by an inflation method.
  • the crosslinkable phenoxy resin composition powder used in Production Example 3 was used without change.
  • M-1 was used as the metal member 101
  • the phenoxy resin CFRP prepreg A of Production Example 1 was used as the bonding resin layer 103A and the FRP layer 102
  • a sample of a metal-CFRP composite body for a bending test having a structure shown in FIG. 10 and a sample of a metal-CFRP composite body for a shear test having a structure shown in FIG. 11 were pressed in a press machine heated to 200 °C at 3 MPa for 3 minutes for production.
  • the thickness of the bonding resin layer 103A was 0.07 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples were produced in the same manner as in Example 1 except that the phenoxy resin CFRP prepreg D of Production Example 4 was used as the bonding resin layer 103A and the FRP layer 102.
  • the thickness of the bonding resin layer 103A was 0.08 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples were produced in the same manner as in Example 1 except that one bonding resin sheet A was used as the bonding resin layer 103 in place of the bonding resin layer 103A, and the phenoxy resin CFRP prepreg D of Production Example 4 was used as the FRP layer 102.
  • the thickness of the bonding resin layer 103 was 0.02 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • a bonding resin powder a was used as the raw material of the bonding resin layer 103 in place of the bonding resin layer 103A, and powder coating of a powder having the same weight as that when the bonding resin powder a became a film having a thickness of 20 ⁇ m was performed on M-1 as the metal member 101. Subsequently, heating was performed in an oven heated to 180 °C for 1 minute and thus the bonding resin powder a was fixed to the metal member 101. Next, together with the plurality of phenoxy resin prepregs D of Production Example 4 which became the FRP layer 102, heating was performed in a press machine heated to 200 °C at a pressure of 3 to 5 MPa for 5 minutes, and thereby two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced. The thickness of the bonding resin layer 103 was 0.02 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • a bonding resin powder b was used as the raw material of the bonding resin layer 103 in place of the bonding resin layer 103A, and powder coating of a powder having the same weight as that when the bonding resin powder b became a film having a thickness of 20 ⁇ m was performed on M-1 as the metal member 101. Subsequently, heating was performed in an oven heated to 180 °C for 1 minute and thus the bonding resin powder b was fixed to the metal member 101, and together with the plurality of phenoxy resin prepregs D of Production Example 4 which became the FRP layer 102, heating was performed in a press machine heated to 240 °C at a pressure of 3 to 5 MPa for 5 minutes, and two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced. The thickness of the bonding resin layer 103 was 0.02 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that the crosslinked phenoxy resin CFRP prepreg E of Production Example 5 was used as the bonding resin layer 103A and the FRP layer 102, and post curing was performed in an oven at 170 °C for 30 minutes after pressing.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • Tg of the matrix resin in the crosslinked phenoxy resin CFRP forming the bonding resin layer 103A and the FRP layer 102 was 83 °C for a cured product in a first cured state before crosslinking and curing and 186 °C for a cross-linked cured product in a second cured state after post curing.
  • the obtained two samples were cooled and then subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 6 except that one bonding resin sheet A was used as the bonding resin layer 103 in place of the bonding resin layer 103A and the plurality of crosslinked phenoxy resin CFRP prepregs E of Production Example 5 were used as the FRP layer 102.
  • the thickness of the bonding resin layer 103 was 0.02 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 6 except that one phenoxy resin prepreg D of Production Example 4 was used as the bonding resin layer 103A and the plurality of crosslinked phenoxy resin CFRP prepregs E of Production Example 5 were used as the FRP layer 102.
  • the thickness of the bonding resin layer 103A was 0.08 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that one phenoxy resin prepreg A of Production Example 1 was used as the bonding resin layer 103A and the plurality of phenoxy resin CFRP prepregs B of Production Example 2 were used as the FRP layer 102.
  • the thickness of the bonding resin layer 103A was 0.08 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that one phenoxy resin CFRP prepreg A of Production Example 1 was used as the bonding resin layer 103A, a plurality of commercially available polyamide resin CFRP prepregs F (using a UD material as a reinforced fiber base material made of carbon fibers) were used as the FRP layer 102, and the press temperature was 230 °C. The thickness of the bonding resin layer 103A was 0.07 mm. The obtained two samples were cooled and then subjected to the bending test and the shear test.
  • a plurality of phenoxy resin CFRP prepregs D of Production Example 4 were laminated and heated and pressed in a press machine heated to 200 °C at a pressure of 5 MPa for 5 minutes and thereby a CFRP molded article having a thickness of 0.4 mm was produced.
  • a sample of a metal-CFRP composite body for a bending test having a structure shown in FIG. 10 and a sample of a metal-CFRP composite body for a shear test having a structure shown in FIG. 11 were produced.
  • M-2 was used as the metal member 101, and the phenoxy resin CFRP prepreg A of Production Example 1 was used as the bonding resin layer 103A and the FRP layer 102, and a sample of a metal-CFRP composite body for a bending test having a structure shown in FIG. 10 and a sample of a metal-CFRP composite body for a shear test having a structure shown in FIG. 11 were produced by performing pressing in a press machine heated to 200 °C at 3 to 5 MPa for 3 minutes. The thickness of the bonding resin layer 103A was 0.07 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 12 except that M-3 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • M-2 was used as the metal member 101, and the crosslinked phenoxy resin prepreg C of Production Example 3 was used as the bonding resin layer 103A and the FRP layer 102, and a sample of a metal-CFRP composite body for a bending test having a structure shown in FIG. 10 and a sample of a metal-CFRP composite body for a shear test having a structure shown in FIG. 11 were pressed in a press machine heated to 120 °C at 1 MPa for 1 minute and thus the bonding resin layer 103A and the FRP layer 102 were brought into a first cured state.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • Tg of the matrix resin in the crosslinked phenoxy resin CFRP forming the bonding resin layer 103A and the FRP layer 102 was 83 °C for a cured product in a first cured state before crosslinking and curing and 186 °C for a cross-linked cured product in a second cured state after post curing. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples shown in FIG. 10 and FIG. 11 were produced in the same manner as in Example 14 except that M-3 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • Tg of the matrix resin in the crosslinked phenoxy resin CFRP forming the bonding resin layer 103A and the FRP layer 102 was 83 °C for a cured product in a first cured state before crosslinking and curing and 186 °C for a cross-linked cured product in a second cured state after post curing.
  • the obtained two samples were cooled and subjected to the bending test and the shear test.
  • M-4 was used as the metal member 101, and the phenoxy resin CFRP prepreg A of Production Example 1 was used as the bonding resin layer 103A and the FRP layer 102, and a sample of a metal-CFRP composite body having a structure shown in FIG. 10 was produced by performing pressing in a press machine heated to 200 °C at 3 MPa for 3 minutes.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • a sample of a metal-CFRP composite body shown in FIG. 10 was produced in the same manner as in Example 16 except that M-5 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • a sample of a metal-CFRP composite body shown in FIG. 10 was produced in the same manner as in Example 16 except that M-6 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • M-4 was used as the metal member 101
  • the crosslinked phenoxy resin CFRP prepreg C of Production Example 3 was used as the bonding resin layer 103A and the FRP layer 102
  • a metal-CFRP composite body having a structure shown in FIG. 10 was pressed in a press machine heated to 200 °C at 3 MPa for 3 minutes, and post curing was then performed in an oven at 170 °C for 30 minutes for production.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • a sample of a metal-CFRP composite body shown in FIG. 10 was produced in the same manner as in Example 19 except that M-5 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • a sample of a metal-CFRP composite body shown in FIG. 10 was produced in the same manner as in Example 19 except that M-6 was used as the metal member 101.
  • the thickness of the bonding resin layer 103A was 0.07 mm.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that no bonding resin layer 103A was provided, a commercially available polyamide resin CFRP prepreg F (using a UD material as a reinforced fiber base material made of carbon fibers) was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and then subjected to the bending test and the shear test.
  • a commercially available polyamide resin CFRP prepreg F using a UD material as a reinforced fiber base material made of carbon fibers
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that no bonding resin layer 103A was provided, a commercially available polycarbonate resin CFRP prepreg G (using a UD material as a reinforced fiber base material made of carbon fibers) was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and then subjected to the bending test and the shear test.
  • CFRP prepreg G using a UD material as a reinforced fiber base material made of carbon fibers
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 1 except that no bonding resin layer 103A was provided and a commercially available polypropylene resin CFRP prepreg H (using a UD material as a reinforced fiber base material made of carbon fibers) was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and then subjected to the bending test and the shear test.
  • CFRP prepreg H using a UD material as a reinforced fiber base material made of carbon fibers
  • No bonding resin layer 103A was provided, M-1 was used as the metal member 101, and the epoxy resin CFRP prepreg K of Production Example 6 was used as the FRP layer 102, and a sample of a metal-CFRP composite body for a bending test having a structure according to FIG. 10 and a sample of a metal-CFRP composite body for a shear test having a structure according to FIG. 11 were produced, and pressed in a press machine heated to 200 °C at 3 MPa for 3 minutes. Then, the samples were subjected to post curing in an oven at 170 °C for 30 minutes. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • a plurality of phenoxy resin CFRP prepregs D of Production Example 4 were laminated and heated and pressed in a press machine heated to 200 °C at a pressure of 5 MPa for 5 minutes, and thereby a CFRP molded article having a thickness of 0.4 mm was produced.
  • the metal member 101 and the FRP layer 102 were bonded by a resin component exuded from the FRP layer 102.
  • the obtained two samples were cooled and then subjected to the bending test and the shear test.
  • a plurality of phenoxy resin CFRP prepregs D of Production Example 4 were laminated and pressed in a press machine heated to 200 °C at a pressure of 5 MPa for 5 minutes and thereby a CFRP molded article having a thickness of 0.4mm was produced.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 5 except that the bonding resin powder c was used as the raw material of the bonding resin layer and the phenoxy resin CFRP prepreg D of Production Example 4 was used as the FRP layer 102.
  • the thickness of the bonding resin layer was 0.016 mm. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 12 except that no bonding resin layer 103A was provided, a commercially available polyamide resin CFRP prepreg F was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 12 except that no bonding resin layer 103A was provided, a commercially available polycarbonate resin CFRP prepreg G was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 12 except that no bonding resin layer 103A was provided, a commercially available polypropylene resin CFRP prepreg H was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 13 except that no bonding resin layer 103A was provided, a commercially available polyamide resin CFRP prepreg F was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 13 except that no bonding resin layer 103A was provided, a commercially available polycarbonate resin CFRP prepreg G was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Two metal-CFRP composite body samples having structures according to FIG. 10 and FIG. 11 were produced in the same manner as in Example 13 except that no bonding resin layer 103A was provided, a commercially available polypropylene resin CFRP prepreg H was used as the FRP layer 102, and the press temperature was 230 °C. The obtained two samples were cooled and subjected to the bending test and the shear test.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 CFRP layer Prepreg used A D D D D D Type of matrix resin A-1 A-1 A-1 A-1 A-1 A-1 A-1 Glass transition point °C 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 186 - Melt viscosity Pa ⁇ s 90 90 90 250 295 Formation Prepreg A Prepreg D Sheet A Powder a Powder b Type of fiber UD Cloth None None None None None Phenoxy proportion

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KR20190095318A (ko) 2019-08-14
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CN110121413A (zh) 2019-08-13
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